CA1162549A

CA1162549A - Oxime ethers, and their production and use

Info

Publication number: CA1162549A
Application number: CA000422239A
Authority: CA
Inventors: Tadashi Ohsumi; Makoto Hatakoshi; Hirosi Kisida
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 1982-03-04
Filing date: 1983-02-23
Publication date: 1984-02-21
Also published as: GB8304056D0; KR840004066A; GB2115812A; IN156256B; EP0089115B1; DK49983A; BR8301058A; NZ203208A; JPS58150559A; EP0089115A1; PH18413A; JPH031297B2; DK49983D0; OA07332A; AU558351B2; DE3360192D1; AU1114783A; KR910008203B1; US4514406A; ZA83749B

Abstract

ABSTRACT

The invention provides a compound of the formula:

Description

1 :7 625~9 OXI~5E ETHERS, AND THEIR PRODUCTION AND USE

The present invention relates to oxime ethers, and their production and use.
The said oxime ethers can be represented by the foxmula:

~ X- ~ 14 13 R

(R6) ~ (R5) m wherein Rl and R2 can be the same or different, and each represents a hydrogen atom, a Cl-C3 alkyl group optionally substituted with halogen, an alkoxyalkyl or alkylthioalkyl group of the formula: R7~Z~(CH2)q~, a C2-C3 alkenyl group, a C2-C4 alkynyl group, a Cl-C2 alkoxy group, a Cl-C2 alkyl-thio group, a phenyl group, a pyridyl group, a furyl groupor a thienyl group, or R1 and R2 may be combined together to form a saturated or unsaturated 5- or 6-membered ring optionally having not more than 2 oxygen or sulfur atoms within the ring; R3 and R4 can be the same or different, and each represents a hydrogen atom or a methyl group; R5 is a methyl group or a halogen atom; R6 is a Cl-C~ alkyl group, a methoxy group, a halogen atom, a trifluoromethyl group or a nitro group; R7 is a methyl group or an ethyl group; X
is an oxygen atom, a sulfur atom or a methylene group; Y
and Z are each an oxygen atom or a sulfur atom; Q is 0 or an integer of 1 to 5, m is 0 or an integer of 1 to 4, n is 0 or an integer of 1 or 2 and q is an integer of 1 or 2.

1 :~ B25~9 In the above definitions, the term "halogen"
includes chlorine, ~romine, iodine and fluorine. Examples of the saturated or unsaturated 5- or 6-membered ring op-tionally having not more than 2 oxygen or sulfur atoms with-in the ring are cyclopentane, cyclohexane, cyclohexene, tetrahydrofuran, tetrahydrothiophene, dithiolan, thian and benzocyclopentanè, etc.
Of the oxime ethers (I), the most preferred are those wherein Rl is a hydrogen atom or a methyl group, R2 is a 10 methyl group, an ethyl group or a vinyl group, R3 and R4 are the same or different, and each represents a hydrogen atom or a methyl group, R6 is a methyl group, a fluorine atom or a chlorine atom, X is an oxygen atom or a methylene group, Y is an oxygen atom, Q is 0 or 1, m is 0 and n is 0.
The oxime ethers (I) can be prepared by various procedures, of which some typical examples are given below.
Procedure A
A compound of the formula:

X ~ Y-cH-(cH2)n-cH 1 (II) IR6),e (R5)m wherein R3, R4, R5, R6, X, Y, Q, m and n are each as defined above and Al is a leaving group such as chlorine, bromine, iodine, mesyloxy or tosyloxy, is reacted with a compound of the formula:

~ ~ ~25~g C=N-O-H (III) wherein Rl and R2 are each as defined above, or its alkali metal salt, to give the ether oxime (I).
The reaction is usually carried out in an inert solvent (e.g. dimethylformamide, dimethylsulfoxlde, tetra-hydrofuran, dimethoxyethane, toluene) in the presence of an acid accepting agent e.g. an alkali metal ~e.g. sodium, potassium), an alkali metal hydride, an alkali metal amide, an alkali metal hydroxide, an alkali metal carbonate (e.g.
potassium carbonate) or an organic base, at a temperature of -30C to the boiling temperature of the solvent, preferably from room temperature to 100C, for a period of 0.5 to 24 hours. In order to accelerate the reaction, a phase transfer catalyst, e.g. benzyltriethylammonium chloride or tetra-n-butylammonium bromide, may be employed. In this case, water may be used as the solvent.
The molar ratio of the compound (II) and the compound (III) is usually 1 : 1 - 3, preferably 1: 1.1 -1.2.
Procedure B
A compound of the formula:

~X ~Y-H ( IV ) (R6)~ (R5)m ~ J 62~9 wherein R5, R6, X, Y, Q and m are each as defined above, or its alkali metal salt, is reacted ~ith a compound of the formula:

~ l3 ~-A2-CH-(CH2) -CH~O-N=C IV) wherein Rl, R2, R3, R4 and n are each as defined above and ~2 is a leaving group e.g. chlorine, bromine, iodine, mesyloxy or tosyloxy, to give the oxime ether (I).
The reaction is normally carried out in an inert solvent (e.g. dimethylformamide, dimethylsulfoxide, tetra-hydrofuran, dimethoxyethane, toluene) in the presence of an acid accepting agent, e.g. an alkali metal (e.g. sodium, potassium), an alkali metal hydride, an alkali metal amide, an alkali metal hydroxide, an alkali metal carbonate (e.g.
potassium carbonate) or an organic base, at a temperature of -30C to the boiling temperature of the solvent, preferably from room temperature to 100C, for a period of 0.5 to 24 hours. In order to accelerate the reaction, a phase transfer catalyst, e.g. benzyltriethylammonium chloride or tetra-n-butylammonium bromide, can be used. In such a case, water may be employed as the solvent.
The molar ratio of the compound (IV) and the compound (V) is usually 1 : 0.33 - 3, preferably l : 0.8 -1.2.
Procedure`C
A compound of the formula:

1 ~ 62~ 9 (~X~3Y-CH- ( CH2 ) n-CH-O NH2 ,e (R5)m wherein R3, R4, R5, R6, X, Y, Q, m and n are each as defined above, or its reactive derivative, is reacted with a compound of the formula:

C=O (VII) wherein Rl and R2 are each as defined above, or its reactive derivative, to give the oxime ether (I).
Examples of reactive derivatives of the compound (VI) are the mineral acid salts (e.g. hydrochloride, sulfate), the organic acid salts, the oxime ethers, etc. Any derivative of the compound (VI) which can afford the compound (VI) itself under the conditions of the reaction system falls within the term "reactive derivative". Examples of the reactive derivative (VII) include the acetals, the ketals, the hemiacetals, the hemiketals, the hydrates, etc. Any derivative of the compound (VII) which can afford the compound (VII) itself under the conditions of the reaction system acts as a "reactive derivative".
The reaction may be carried out in the presence or absence of an inert solvent (e.g. water, benzene, toluene, carbon tetrachloride, chloroform, ethylene chloride, 1 ~ 6~5~9 methylene chloride) and/or an acid (e.g. hydrochloric acid, sulfuric acid, p-toluenesulfonic acid) or a base (e.g.
sodium hydroxide, potassium hydroxide, potassium carbonate, triethylamine, pyridine), usually at a temperature of -30C
to the boiling temperature of the solvent, preferably from room temperature to 100C, for a period of 0.5 to 24 hours.
The molar ratio of the compound (VI) and the compound (VII) is normally 1 : 1 - 20, preferably 1 1.2.
In the above procedures, the recovery of the oxime ether (I) thus produced from the reaction mixture and the purification of the recovered oxime ether (I) may be carried out by per se conventional procedures. For instance, the purification can be achieved by chromatography, distil-lation, etc.
The oxi.me ether (I) has optical isomers with respect to the groups R3 and R4 and geometrical isomers with respect to the groups Rl and R2, and all such isomers are included within the scope of the invention.
The compound (II) as one of the starting materials may be produced by per se conventional procedures, of which typical examples are shown in the following formulas:
Route I:-1 :1 6~5~ 9 ~ X ~ Y-H IR

(R6)~ (R5)m (ii) Br-CH (CH2)n-C=O
(IV) (VIII) ~ X ~ Y-CH-(CH2) -C-O - 4 (R6),e (R5)m (IX) ~ X ~ Y-CH-(C~2) -CH-OH 3 ~ (II: A1 = Br) (R6)~ (R5)m (X) wherein R3, R4, R5, R6, X, Y, Q, m and n are each as defined above, and R7 is a group of the formula: -OR8 (wherein R8 is a Cl-C3 alkyl group) when R3 is a hydrogen atom, but R7 is a methyl group when R3 is a methyl group.
Route II:-X ~ Y-H + A3-CH-(CH2)n-cH-A3 ~ Al =
(XI) halogen) (R6)~ (R5)m (IV) wherein R3, R4, R5, R6, X, Y, ~, m and n are each as defined above and A3 is a halogen atom.

-I 1 6~5~9 The compound (III) is known or can be prepared by per se conventional procedures (cf. Org.Synth., Coll. Vol.
II, 313 (1943).
The compound (IV) is known or can be prepared by per se conventional procedures (cf. Angew.Chem., 52, 915 (1938); Japanese Patent Publn. (unexamined) No~ 62033/1980).
The compound (V) may be prepared by per se conventional procedures, of which typical examples are as follows:
Route I:-ClCH2CH2Cl + CH3CH2CH=NOH

Phase transfercatalyst ClCH2CH20-N=CHCH2CH3 50 ~ NaOH
(V: Rl = H; R2 = C2H ;
n3 o)H; R4 = H; A2 = ~1;

Route II:-3 \ / 2 3 2 CH OH >

CH CH
1 3 TsCl/Pyridine I 3 HO-CHCH20N=CHCH2CH3 '~ TsO-CHCH20N=CHCH2CH3 (V: Rl = H; R = C2H5;
3 ; 4 C~;
A2 = TsO; n = 0 The compound (VI) can be prepared by per se conventional procedures (cf. 3.0rg.Chem., 28, 1604 (1963);

Japanese Patent Publns. (unexamined) Nos. 144571/1978 and ~ 1 ~2549 147014/1978), of which a typical example is shown below:

~,,,N-OH + (~X4.~Y-CH- (CH2) -CH-A

(R6),Q (R5)m (II) Base ~ ~Y-CH- (CH2 ) n~CH~~~

,e (R5~m 0 (XII ) NH2NH2 ~ X~ ( 2) O NH
or NH2OH ~ ~ n 2 (R6)~ (R5)m (VI) wherein R3, R4, R5, R6, X, Y, Al, ~, m and n are each as defined above.
Some practical embodiments of the procedures for preparation of the oxime ether (I) are shown in the following Examples.
Example 1 (Production of Compound No. 2 according to Procedure A) Pro~ionaldoxime (0.73 g; 10.0 mmol) was dissolved in dimethylformamide (10 ml), and the resulting mixture was stirred at an internal temperature of 10C under ice-cooling, followed by the addition of sodium hydride (0.24 g; 10.0 mmol).

1 J 62~l9 ~fter completion of the reaction, stirring was continued for

2 hours, and a solution of 2~(4-phenoxyphenoxy~ethyl tosylate (3.20 g; 8.33 mmol) in dimethylformamide (10 ml) was added dropwise thereto. The resultant mixture was stirred at room temperature overnight, poured into water and extracted with ethyl acetate. ~he extract was washed with water and concentrated. The residue was purified by silica gel column chromatography using benzene as an eluant to give 1.50 g of Compound No. 2 as a pale yellow oily substance in a yield of 52.6 %. nD = 1.5577.
Example 2 (Production of Compound No. 24 according to Procedure A) 2-Hydroxyiminotetrahydrothiophene (0.50 g; 4.27 mmol) was dissolved in dimethylformamide (10 ml), and the resulting mixture was stirred at an internal temperature of 10C under ice-cooling, followed by the addition of sodium hydride (0.10 g; 4.27 mmol). After completion of the reaction, stirring was continued for 2 hours, and a solution of l-bromo 2-(4-phenoxyphenoxy)ethane (1.04 g; 3.56 mmol) in dimethylformamide (5 ml) was added dropwise thereto. The resultant mixture was stirred at room temperature overnight, poured into water and extracted with ethyl acetate. The extract was washed with water and concentrated. The precipitated crystals were collected, washed with n-hexane and dried to give 0.80 g of Compound No. 24 in a yield of ~2.6 ~. M.P., 107.6C.
Example 3 (Production of Compound No. 97 according to Procedure B).
4-Phenoxyphenol (1.86 g; 10.0 mmol) was dissol~ed in dimethylformamide (10 ml), and the resulting mixture was stirred at an internal temperature of 10C under ic~-cooling, followed by the addition of sodium hydride (0.24 g; 10.0 mmol).
A~ter completion of the reaction, stirring was continued for 2 hours, and a solution of 0- {3-(p-toluenesulfonyloxy)-propyl} propionaldoxime (2.28 g; 8.0 mmol) in dimethylform-amide (10 ml) was added dropwise thereto. The resultant mixture was stirred at 80 - 100C overnight, poured into water and extracted with ethyl acetate. The extract was washed with water and concentrated. The residue was purified by silica gel column chromatography using benzene as an eluant to give 1.20 g of Compound No. 97 as a pale yellow oily substance in a yield of 40.1 %. nD3-0 ~ 1.5584.

Example 4 (Production of Compound No. 9 according to Procedure C) A 30% aqueous solution of chloroacetaldehyde (0.52 g) was added dropwise to a solution of 0- f (4-phenoxy-phenoxy)ethyl} -hydroxylamine (0.25 g; 10.0 mmol) in chloro-~orm (5 ml) over 10 minutes, followed by stirring at room temperature overnight. The reaction mixture was poured into water, dried over anhydrous sodium sulfate and concentrated, whereby an oily substance was obtained, whlch was then purified by silica gel column chromatography using methylene chloride as an eluant to give 0.24 g of Compound No. 9 as a transparent oily substance in I 1 625~

a yield of 78.5%. n22-5 = 1.5712.

Example 5 (Production of Compound No~ 2 according to Procedure C) Compound No. 5 (prepared in the same manner as in Example 1 but using acetoxime in place of propionaldoxime) (0.05 g; 0.18 mmol) and propionaldehyde (0.02 g; 3.5 mmol) were dissolved in methanol (1 g) and, after the addition of one drop of conc. sulfuric acid, the resultant mixture was refluxed for 3 hours to complete the reaction. The reaction mixture was cooled to room temperature and water (20 ml) was added thereto, followed by extraction with chloroform (10 ml) twice. The extract was dried over anhydrous sodium sulfate and concentrated to give an oily product. Gas chromatographic analysis showed the product to contain 88 of Compound No. 2.
In the same manner as above, the oxime ethers (I) were prepared of which some examples are shown in Tahle 1.

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It is already known that tne organic phosphorus series insecticides, organic chlorine series i~secticides and carbamate series inseetieides largely contribute to the prevention of harmful insects. Some of these insecticides however, exhibit a high phytotoxicity so that their residual effects have posed a serious problem in the abnormal eeo-system of the insects. Further, a resistivity to the insecticides has recently become noticed in certain insects such as house flies, planthoppers, leafhoppers, rice borers, etc.
In order to solve these drawbacks of conventional insecticides, an extensive study has been carried out to provide improved inseetieides whieh show high preventative effects at low concentration attributable to a juvenile hormone-like controlling aetivity and, as a result, it has now been found that the oxime ethers (I) of the invention are useful for the control of insects in agricultural fields, forest lands, granaries, stored produets and sanitary facilities, etc.
An insectieide having a juvenile hormone-like controlling activity is available under the trademark "methoprene" (U.S. patents 3,904,662 and 3,912,815). This known insecticide is still not satisfactory.
The oxime ethers (I) of the invention show a juvenile hormone-like controlling effeet and therefore ean be used in low eoncentrations for the control of a variety of insects belonging to Hemiptera, Lepidoptera, Coleoptera, I 1 625~9 Diptera, Dictyoptera, Orthoptera, Homop~era, Hymenoptera and Aphaniptera in agricultural fields, forest lands, granaries, stored products and sanitary facilities, etc., of wh~ch specific examples are as follows:
1. Hemiptera:-smaller brown planthopper (Laodelphax striatellus), brown planthopper (~ E~ ), white-backed planthopper (Sogatella furcifera), green rice leafhopper (Nephotettix cincticePs), rice stink bug (Lagynotomus elongatus), common green stink bug (Nezara antennata), white-spotted bug (Eysarcaris _ntralis), green peach aphid (Myzus persicae), cotton aphid (Aphis gossypii), cabbage aphid (srevicoryne brassicae), cottony cushion scale (Icerya purchasi), citrus mealy bug (Plano occus citrl), arrowhead scale (Unaspis yanonensis), etc.
2. Lepidoptera:~
to~acco cutworm (Spodoptera litura), rice stem borer (Chilo suppressalis), grass leaf roller (Cnaphalocrocis medinalis), wax moth (Galleria mellonella), diamond back moth (Pluttella xylostella), smaller tea tortrix (Adoxophves sp.), common white (Pieris rapae), cabbage army-worm (Mamestra brassicae), armyworm (Pseudaletia separate), etc.
3. Coleoptera:-- 2~ -~ 1 625~

varied carpet beetle (Anthrenus ~erbasci), lyctus powder-post beetle (Lyctus brunneus), rice leaf beetle (Onlema or~zae), rice plant weevil (Echinocnemus squameus), 28-spotted lady beetle (Henosepilachna vigintioctopunctata), cupreous beetle (Anomala cuprea), japanese beetle (Popilla japonica), tobacco beetle (Lasioderma serricorne), etc.

4. Diptera:-housefly (Musca domestica), melon fly (Dacus cucurbitae), common mosquito (Culex pipiens pallens), yellow fever mosquito (~edes aegypti), malaria mosquito (Anopheles sp.), etcO

5. Dictyoptera:-German cockroach (Blattella germanica), smoky brown cockroach (Periplaneta fuliginosa), etc.

In practical application as insect control agents, the oxime ethers (I) are used in the form of appropriate compositions e.g. emulsifiable concentrates, dusts, granules, wettable powders, fine granules and aerosols, and the content of the oxime ethers (I) in such compositions is usually from about 0.1 to 99.9% by weight, preferably from about 2.0 to 80.0 % by weight.
~ he compositions can be formulated in per se conventional manners by mixing at least one of the oxime ethers (I) with an appropriate solid or liquid carrier(s) or diluent(s) with or without an appropriate I ~ ~2~9 adjuvant(s) (e.g. surfactants, adherents, dispersants, stabilizers) for improving the dispersibility and other properties of the active ingredient in use.
Examples of the solid carriers or diluents are clays (e.g. kaolin, bentonite, fuller's earth, pyrophyllite, sericite), talcs, other inorganic materials (e.g. hydrated silica, pumice, diatomaceous earth, sulfur powder, active carbon) in fine powders or powdery form.
Examples of the liquid carriers or diluents are alcohols (e.g. metha~ol, ethanol), ketones (e.g. acetone, methyl ethyl ketone), ethers (e.g. diethyl ether, dioxane, cellosolve, tetrahydrofuran), aromatic hydrocarbons (e.g.
benzene, toluene, xylene, methylnaphthalene), aliphatic hydrocarbons (e.g. gasoline, kerosene, lamp oil), esters, nitriles, acid amides (e.g. dimethylformamide, dimethyl-acetamide), halogenated hydroca~bons (e.g. dichloroethane, trichloroethylene, carbon tetrachloride), etc.
Examples of the surfactants are alkylsulfates, alkylsulfonates, alkylarylsulfonates, polyethylene glycol ethers, polyhydric alcohol esters, etc. Examples of the adherents and dispersants may include casein, gelatin, starch powder, carboxymethyl cellulose, gum arabic, alginic acid, liqninsulfonate, bentonite, molasses, polyvinyl alcohol, pine oil and agar. PAP (isopropyl acid phosphates mixture), TCP (tricresyl phosphate), tolu oil, epoxydized oil, various surfactants, various fatty acids and their esters, etc., may be employed as the stabilizers.

l 1 6~

In addition, the said compositions may contain conventional insecticides, insect growth inhibitors, acaricides, nematocides, fungicides, herbicidas, plant growth regulators, fertilizers, soil improvers, etc. Particularly when employed in conjunction with conventional insecticides, a broad spectrum o~ activity or a more immediate effect on very heterogeneous populations is provided. Examples of the conventional insecticides include organic phosphorus compounds (e.g. Fenitrothion* (0,0-dimethyl-0-(3-methyl-4-nitrophenyl)-phosphorothioate), Malathion* (S-[1,2-bis(ethoxycarbonyl)-ethyl] 0,0-dimethylphosphorothioate), Dimethoate* (0,0-dimethyl-S-(N-methylcarbamoylmethyl)phosphorodithioate), Salithion* (2-methoxy-4~-1,3,2-benædioxaphosphorin-2-sulfide), Diazinon* (0,0-diethyl-0-(2-isopropyl-6-methyl-4-pyrimydinyl) phosphorothioate), Dipterex* (2,2,2-trichloro-1-hydroxyethyl-0,0-dimethylphosphonate), Dichlorvos* (0-(2,2-dichlorovinyl)-0,0-dimethylphosphate), etc.), carbamate compounds (e.~. MPMC
(3,4-dimethylphenyl N-methylcarbamate), MTMC (m-tolyl N-methylcarbamate), BPMC (2-sec-butylphenyl N-methylcarbamate), Carbaryl* (l-naphthyl N-methylcarbamate), etc.) and pyrethroid compounds (e.g. Permethrin* (3-phenoxy-benzyl-d,Q-cis,trans-3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropanecarboxylate), Fenvalerate* (~-cyano-m-phenoxy-benzyl ~-isopropyl-p-chloro-phenylacetate, etc.).
The oxime ethers (I) of the invention formulated into an appropriate composition may be applied in a suitable application method such as spraying, smoking, soil treat-*Trademark I 1 62 ~A 9 ment, soil surface treatment or in combination with animal feed.
Some practical embodiments of the composition for the control of insects according to the invention are illustratively shown in the following Formulation Examples wherein % and part(s) are by weight.
Formulation Example 1 Each of Compound Nos. 1 to 122 (20 parts), an emulsifier (a mixture of polyoxyethylene-styrenated phenyl ether, polyoxyethylene-styrenated phenyl ether polymer and an alkylarylsulfonate) (20 parts) and xylene (60 parts) were thoroughly mixed to make an emulsifiable concentrate containing the active ingredient in a concentration of 20 %.
Formu~ation Example 2 Each of Compound Nos. 1 to 122 (20 parts) and an emulsifier (sodium laurylsulfate) (5 parts) were thoroughly mixed, and diatomaceous earth (300 mesh) (75 parts) was added thereto, and the resultant mixture was thoroughly mixed in a pulverizer to make a wettable powder containing the active ingredient in a concentration of 20 %.
Formulation Example 3 Each of Compound Nos. 1, 2, 29 or 90 (3 parts) was dissolved in acetone (20 parts), talc (300 mesh3 (97 parts) was added thereto, and the resultant mixture was thoroughly mixed in a pulverizer. Then acetone was eliminated by evaporation to give a dust containing the active ingredient in a concentration of 3 %.

1 ~ 62~ 9 Formulation Example 4 Each of Compound Nos. 2 or 29 (5 parts~, a dispersant (calcium ligninsulfonate) (2 parts) and kaolin (93 parts) were thoroughly mixed in a pulverizer. To the resultant mixture, water was added in an amount of 10 ~, and the resulting mixture was thoroughly kneaded and granulated ~y the aid of a granulator, followed by drying to give granules containing the active ingredient in a concentration of 5~.
Eormulation Example 5 Compound No. 2 (2 parts), a dispersant (calcium lingninsulfonate) (2 parts) and kaolin (96 parts) were mixed in a pulverizer. Water was added to the resultant mixture in an amount of 10 ~. The resulting mixture was mixed well and granulated by the aid of a granulator. The granules were dried to give fine granules containing the active ingredient in a concentration of 2 %.
Formulation Example 6 Each of Compound Nos. 2 or 29 (5 parts), xylene (7 parts) and deodered kerosene (8 parts) were mixed well and charged to an aerosol container and, after setting up a valve thereon, a propellant (liquid petroleum gas) (80 parts) was charged through the valve under pressure to give an aerosol.
The ~ollowing Examples show some typical test data indicating the excellent insect control activity of the oxime ethers (I). The compounds used for comparison are as follows:

I 1 6~5~9 Compound No. Chemical structure Remarks A ~ O ¦ Commercially available / ~ ~ ~O/ \ insecticide "~ethoprene"

B CN ~ Commercially OC ~ available insecticide O ~ O ~ ~ "Fenvalerate"
Cl C S CH3 Commercially (CH3O)2P-O ~ N02 available "Fenitrothion"

Test Example 1 Pupae of the wax moth (Galleria mellonella) were collected within 20 hours from pupation. According to the Schneiderman's method (J. Insect Physiol., 11, 1641 (1965)), a puncture of about 1 mm2 was made in the right side of the thoracic dorsum of each pupa, and the wound was sealed with a predetermined amount of the test compound dissolved in a mixture of paraffin wax and peanut oil.

The medicated pupae were kept at 28C in a pyrostat.
The pupal cuticule i 1 62 5A 9 at the medicated part was peeled off before emer~ence, and observation was made to examine the formation of the pupal cuticule, from which the average rate of reaction to~the test compound was determined, and the dose of the test compound for 50 ~ inhibition of the metamorphosis (ID50) was calculated. The results are shown in Table 2.
Table _ Test compound ID50 (~g/pupa) 1 < O .001 2 <0.001 11 <O .001 29 <0.001 <O . 001 A ¦ 2.2 Test Example 2 An emulsifiable concentrate prepared according to Formulation Example 1 was diluted with water to make a 400 fold dilution. The dilution (0.7 ml) was added to 100 ml of distilled water. Last instar larvae of common mos~uito (Culex pipiens pallens) were released therein and reared for 7 days until their emergence. The rate of emergence was observed (two replications). The results are shown in Table :~ .

1 1 62~ ~

Table 3 I
Test compound Concentration Rate of emergence No. (ppm) ! 14 3.5 iO
3.5 10 16 3.5 10 1 17 3.5 'O
i 18 3.5 ~O
19 3.5 10 22 3.5 O
24 3 5 oo 3.5 O

! 32 3.S O
33 !3,5 O
34 13.5 O
3.5 O
36 3.5 O
37 13.5 O
38 ,3.5 O
39 3.5 O
3.5 O

42 ~3.5 O
43 13.5 O
44 13.5 O
13.5 O
46 13.5 1_ O

1 1 52~ 9 (Continued) Test compound ¦ Concentration Rate of emergence No. _ ! (ppm3 (%) 47 ¦ 3 A 5 0 48 1 3.5 0 49 1 3.5 0 j 3.5 0 51 1 3.5 0 57 3.5 0 58 3.5 0 59 3.5 0 1 3.5 0 61 1 3.5 0 62 3.5 0 63 3,5 0 64 3.5 ~ 0 1 65 3.5 0 66 3.5 0 ' 67 3.5 0 ! 68 3.5 0 69 3.5 0 3.5 0 71 3.5 0 72 3.5 0 /~ 3.5 0 1 74 3.5 0 1 75 3.5 0 76 3.5 0 77 3.S 0 78 3.5 0 79 3.5 0 3.5 0 i 81 3.5 0 82 3.5 0 83 1 3.5 0 84 1 3.5 0 j' ' 3.5 0 86 ~ 3.5 0 87 ~ 3.5 0 88 j 3.5 0 89 1 3.5 0 1 3.5 0 91 1 3.5 0 92 ~ 3.5 0 93 3.5 0 94 3.5 0 ~ ~ 625~1~

(Continued) . _ Test compound ConcentrationRate of emergence No. (ppm) (%) __ 3.5 0 96 3.5 0 97 3.5 0 98 3.5 0 99 1 3.5 0 100 j 3.5 0 101 1 3.5 0 102 1 3.5 0 103 3.5 0 104 3.5 0 105 3.5 0 106 3.5 0 107 3.5 0 108 j 3.5 0 109 1 3.5 0 110 i 3.5 0 3.5 0 112 1 3.5 0 1113 ! 3-5 0 j114 ~ 3.5 0 ¦115 ! 3.5 0 118 , 3.5 0 119 3.5 0 120 ' 3.5 0 121 ~ 3.5 0 122 1 3.5 .. . _ O
._ Untreated Test Example 3 An emulsifiable concentrate prepared according to Formulation Example 1 was diluted with water to a designed dilution. The dilution (0.5 ml) was added to 100 ml of distilled water. Twenty last instar larvae of common mosquito (Culex pipiens pallens) were released therein and reared for 7 days until their emergence. The 50 ~ emergence inhibition concentration (IC50) was determined (two repli-cations). The results are shown in Table 4 wherein PI50 corresponds to -log IC50.
Table 4 Test Compound No. PI50 7 4.4 11 6.6 12 4.1 14 14.0 15.1 21 '4'7 i 23 j4.5 j 24 16.6 1 25 14.5 1 26 !5.0 ! 29 !6.5 ! 36 !4.0 ! 39 i,4.0 41 4.1 ' 42 . 4.0 ',51 4.6 4.4 56 3.9 57 4.8 4.3 64 3.9 4.7 66 3.9 68 4.3 ~ 69 4.5 f 78 4.0 87 4.0 7.6 97 4.3 101 5.8 !10 2 6.2 , 106 4.2 1 115 4.4 116 4.9 . ._ ... __ I

I ~ 6~54g Test Example 4 In the same manner as in Test Example 2 but rear-ing yellow fever mosquito (Aedes aegypti) instead of common mosquito (Culex pipiens pallens), the rate of emergence was observed (two replications). The results are shown in Table 5.
Table 5 Test compound ¦ ConcentrationRate of emergence~
No. ¦ (ppm) (%) 12 3.5 0 14 3.5 0 16 3.5 0 231 3.5 0 24 3.5 0 3.5 0 26 3.5 0 ~9 3.~ 1 0 38 3.5 i 0 39 3.5 0 54 3.5 , 0 87 3.5 0 3.5 0 92 3.5 0 j 101 3.5 0 j 102 3.5 0 112 3.5 0 116 3.5 0 ~ntreated 87.5 1 ~ ~2~49 Test Exa~ple 5 In the same manner as in Test Example 3 but rear-ing yellow fever mosquito (Aedes aegypti) instead of common mosquito (Culex pipiens pallens), the 50 % emergence inhibi-tion concentration (IC50) was examined (two replications).
The results are shown in Table 6 wherein PI50 corresponds to -log IC50.
Table 6 ~Test Compound No. PI50 2 7.2 101 7.4 102 7.6 .. __ ... ._.___ Test Example 6 Powdered animal feed (2 g) was thoxoughly mixed with bran (14 g). An emulsifiable concentrate prepared according to Formulation Example 1 was diluted with water to a predetermined concentration and added to the above mixture.
The resultant mixtuxe was stirred well to make an artificial culture. Thirty larvae of housefly (Musca domestica) were reared therein until their pupation. The obtained pupae were placed into a plastic cup, and the rate of emergence was determined. The emergence inhibition (%) was calculated according to the followillg equation:

Emergence inhibition = (1 Rate of emergence in treated plot ) x 100 Rate of emergence in untreated plot The results axe shown in Table 7.

13625~9 Table 7 ¦ Test compound Emergence inhibition No. (%) 3 ppm 1 ppm O . 3 ppm oo loo loo 2 loo loo loo 4 loo 97 80 ! 5 loo loO 92 i 25 97 33 8 1 28 loo loo loo 29 loO loO IloQ
1 33 loo 96 79 ! 36 79 33 24 41 loo go 1 5 : 48 loo loo loo 54 lOo loo loo 57 loO 96 73 87 40 s 63 97 62 o 64 84 42 o 66 lOo . 40 42 ~ 69 97 38 14 ! 70 93 25 o '` 72 73 22 4 i 87 loo 38 o 88 100 100 ~6 89 loo 97 26 03 loo loo loo 105 loO 93 54 106 lOo loo 52 116 loo loo loo 120 92 74 o 1 ~ ~25~ ~

Test Exampl_ 7 An emulsifiable concentrate prepared according to Formulation Example 1 was diluted with water to a predetermined concentration. The resultant dilution (50 ml) was added to feed for domestic fowl (100 g) and thoroughly mixed. The thus obtained mixture was fed to groups of fowl (each group consisting of three animals) at a daily dose of 100 g/fowl for 2 days, whereupon their droppings were collected. Two hundred eggs of ~he housefly (Musca domestica) were incubated in the droppings until their pupation. The obtained pupae were placed into another container, and the 50 % emergence lnhibition concentration (IC50) was examined. The results are shown in Table 8.

Table 8 Test Compound No. 50 (PP ) 1 21:6 29 1.2 2.2 Test Example 8 Fifty imagoes each of male and female houseflies (Musca domestica) were put in a cage. Separately, powdered feed (2 g), bran (14 g) and water (28 ml) were thoroughly mixed to make an artificial culture and one hundred 4-day-old housefly larvae were reared therein. An emulsifiable concentrate of Compound No. 29 prepared according to Formulation Example 1 as well as its mixture I 1 625~9 with Compound B ("Fenvalerate") and Compound C ("Fenitrothion") was sprayed in the case and on the culture at a spray volume of 20 ml. After the spraying, the culture was put in the cage, and the numbers of the imagoes within the cage were observed with the lapse of days and evaluated in terms of "corrected density index", which was calculated according to the following equation:

Number of imago Number of imago Corrected before treatment x after treatment density = in untreated plot in tr_ated plot x 100 index Number of imago Number of imago after treatment x before treatment in untreated plot in treated plot The results are shown in Table 9.
Table 9 Com-Concen- Corrected density index pound tration _ . ~
No.(ppm) 1 day 2 days ¦5 days 16 days ¦22 days 29 5 98 98 1 100 14 l,~.3 B 10 67 73 ¦ 74 46 i 48 ¦ 29JB5/10 71 69 67 6 . 2

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A compound of the formula:

wherein R1 and R2 can be the same or different, and each represents a hydrogen atom, a C1-C3 alkyl group optionally substituted with halogen, an alkoxyalkyl or alkylthioalkyl group of the formula: R7-Z-(CH2)q-, a C2-C3 alkenyl group, a C2-C4 alkynyl group, a C1-C2 alkoxy group, a C1-C2 alkyl-thio group, a phenyl group, a pyridyl group, a furyl group or a thienyl group, or R1 and R2 may be combined together to form a saturated or unsaturated 5- or 6-membered ring optionally having not more than 2 oxygen or sulfur atoms within the ring; R3 and R4 can be the same or different, and each represents a hydrogen atom or a methyl group; R5 is a methyl group or a halogen atom; R6 is a C1-C4 alkyl group, a methoxy group, a halogen atom, a trifluoromethyl group or a nitro group; R7 is a methyl group or an ethyl group; X is an oxygen atom, a sulfur atom or a methylene group; Y and Z
are each an oxygen atom or a sulfur atom; ? is 0 or an integer of 1 to 5, m is 0 or an integer of 1 to 4, n is 0 or an integer of 1 or 2 and q is an integer of 1 or 2.

2. A compound according to claim 1, wherein R1 is a hydrogen atom or a methyl group, R2 is a methyl group, an ethyl group or a vinyl group, R3 and R4 can be the same or different, and each represents a hydrogen atom or a methyl group, R6 is a methyl group, a fluorine atom or a chlorine atom, X is an oxygen atom or a methylene group, Y is an oxygen atom, ? is 0 or 1, m is 0 and n is 0.

3. A compound according to claim 1, wherein R1, R3 and R4 are each a hydrogen atom, R2 is a methyl group, x and Y are each an oxygen atom, n is 0, m is 0 and ? is 0.

4. A compound according to claim 1, wherein R1, R3 and R4 are each a hydrogen atom, R2 is an ethyl group, X and Y are each an oxygen atom, n is 0, m is 0 and ? is 0.

5. A compound according to claim 1, wherein R1, R3 and R4 are each a hydrogen atom, R2 is a methyl group, R6 is a fluorine atom at the 3-position, X and Y
are each an oxygen atom, n is 0 and m is 0.

6. A compound according to claim 1, wherein R1, R3 and R4 are each a hydrogen atom, R2 is an ethyl group, R6 is a fluorine atom at the 3-position, X and Y
are each an oxygen atom, n is 0 and m is 0.

7. A compound according to claim 1, wherein R1, R3 and R4 are each a hydrogen atom, R2 is an ethyl group, X is a methylene group, Y is an oxygen atom, n is 0, m is 0 and ? is 0.

8. A compound according to claim 1, wherein R1, R3 and R4 are each a hydrogen atom, R2 is an ethyl group, X and Y are each an oxygen atom and R6 is fluorine atoms at the 3 and 5-positions, n is 0 and m is 0.

9. A compound according to claim 1, wherein R1, and R3 are each a hydrogen atom, R2 and R4 are each a methyl group, R6 is a fluorine atom at the 3-position, X and Y are each an oxygen atom, n is 0 and m is 0.

10. A compound according to claim 1, wherein R1 and R3 are each a hydrogen atom, R2 is an ethyl group, R4 is a methyl group, R6 is a fluorine atom at the 3-position, X and Y are each an oxygen atom, n is 0 and m is 0.

11. A compound according to claim 1, wherein X
and Y are each an oxygen atom, R1 is a hydrogen atom, R2 is an ethyl group, R3 is a hydrogen atom, R4 is a methyl group, n is 0, m is 0 and ? is 0.

12. A process for preparing a compound according to claim 1, which comprises either: (A) reacting a compound of the formula:

wherein R3, R4, R5, R6, X, Y, ?, m and n are each as defined in claim 1 and A1 is a leaving group selected from chlorine, bromine, iodine, mesyloxy and tosyloxy, with a compound of the formula:

wherein R1 and R2 are each as defined above, or an alkali metal salt thereof; or (B) reacting a compound of the formula:

wherein R5, R6, X, Y, ? and m are each as defined in claim 1, or an alkali metal salt thereof with a compound of the formula:

wherein R1, R2, R3, R4 and n are each as defined above and A2 is a leaving group selected from chlorine, bromine, iodine, mesyloxy and tosyloxy; or (C) reacting a compound of the formula:

wherein R3, R4, R5, R6, X, Y, ?, m and n are each as defined in claim 1, or a reactive derivative thereof, with a compound of the formula:

wherein R1 and R2 are each as defined above, or a reactive derivative thereof.

13. A method for controlling insects which comprises applying an insecticidally effective amount of the compound according to claim 1 to said insects or to a surface with which the insects will come into contact.

14. A method according to claim 13 wherein the compound according to claim 1 is applied in combination with animal feed.